J Porous Mater (2011) 18:205210 DOI 10.

1007/s10934-010-9371-7

Sorption studies of CO2, CH4, N2, CO, O2 and Ar on nanoporous aluminum terephthalate [MIL-53(Al)]
Phani Rallapalli K. P. Prasanth Dinesh Patil Rajesh S. Somani R. V. Jasra H. C. Bajaj

Published online: 21 March 2010 Springer Science+Business Media, LLC 2010

Abstract Aluminum terephthalate, MIL-53(Al), metal organic framework synthesized hydrothermally and puried by solvent extraction method was used as an adsorbent for gas adsorption studies. The synthesized MIL-53(Al) was characterized by powder X-Ray diffraction analysis, surface area measurement using N2 adsorptiondesorption at 77 K, FTIR spectroscopy and thermo gravimetric analysis. Adsorption isotherms of CO2, CH4, CO, N2, O2 and Ar were measured at 288 and 303 K. The absolute adsorption capacity was found in the order CO2[CH4[ CO[N2[Ar[O2. Henrys constants, heat of adsorption in the low pressure region and adsorption selectivities for the adsorbate gases were calculated from their adsorption isotherms. The high selectivity and low heat of adsorption for CO2 suggests that MIL-53(Al) is a potential adsorbent material for the separation of CO2 from gas mixtures. The high selectivity for CH4 over O2 and its low heat of adsorption suggests that MIL-53(Al) could also be a compatible adsorbent for the separation of methane from methaneoxygen gas mixtures. Keywords MOF Adsorbent Aluminum terephthalate MIL-53(Al) Gas separation

1 Introduction Carbon dioxide is one of the major greenhouse gases accounting for the global warming effect [1]. Adsorption employing CO2 selective zeolite and activated carbon type adsorbent is a potential process for mitigating this problem. However, development of material possessing high CO2 adsorption capacity and selectivity is the key to commercial success of adsorption processes. The major adsorbents reported for this application include zeolites, activated carbons [24], functionalized mesoporous silica [5] and hydrotalcite [6, 7]. Metalorganic framework (MOF) type materials have attracted attention due to their higher surface areas compared to conventional adsorbents [8, 9]. Due to their textural attributes, MOFs are also being studied for size selective molecular catalysis [10], hydrogen and methane storage [1114] and gas adsorption applications [1519]. However, the major limitation of the MOFs is the lower thermal stability compared to zeolites and carbon based adsorbents which restrict their industrial applications. The MIL-n (materials of the institute Lavoisier) series rst synthesized by Fereys group [20] is able to adjust its cell volume in a reversible manner to optimize interactions between the guest molecules and the framework, with no evidence of bond breaking. This phenomenon named as breathing in MOF, due to their breathing character upon adsorption of water and CO2 have attracted much attention [2123]. The adsorption studies of CO2, CH4, and H2 in MIL53(Al) have been reported [2426]. To the best of our knowledge, adsorption studies of other industrially important gases such as CO, N2, Ar, and O2 in MIL-53(Al) are not reported till date. In the present study, the adsorption measurements of CO2, CH4, CO, N2, O2 and Ar on

P. Rallapalli K. P. Prasanth D. Patil R. S. Somani H. C. Bajaj (&) Discipline of Inorganic Materials and Catalysis, Central Salt and Marine Chemicals Research Institute (CSMCRI), Council of Scientic & Industrial Research (CSIR), G.B. Marg, Bhavnagar, Gujarat 364 002, India e-mail: hcbajaj@csmcri.org Present Address: R. V. Jasra R & D Centre, Reliance Industries Limited, Manufacturing Division, Vadodara, Gujarat 391 346, India

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MIL-53(Al) were performed at 288 and 303 K up to 1 bar. The heat of adsorption, Henrys constants and selectivities in the Henrys region of the gases were calculated. The potential of MIL-53(Al) as an adsorbent for separation of CO2 and CH4 from other gas mixtures is discussed.

2 Experimental 2.1 Materials Aluminum (III) nitrate, Al(NO3)39H2O (98% pure, s. d. Fine Chemicals, India), terephthalic acid, H2BDC (98% pure, Aldrich) and deionized water were used for the hydrothermal synthesis of nanoporous MIL-53(Al). Ar, CO2, CO, CH4, N2, O2 and He gases used for the adsorption studies and surface area measurement were of ultra high purity grade (99.999%; Inox India Ltd). 2.2 Synthesis of MIL-53(Al) Al(NO3)39H2O (13 g), terephthalic acid (2.88 g) and deionized water (49 mL) were placed in a 75 mL. Teonlined steel autoclave, and the autoclave was heated at 493 K for 72 h. After completion of reaction, the autoclave was cooled and the white powder formed was ltered, washed with distilled water (4 9 50 ml) until pH of ltrate is *7, and dried overnight at 353 K in air. The dry powder designated as MIL-53(Al)as, containing unreacted free terephthalic acid in the tunnels, was puried by solvent extraction method as previously reported and abbreviated as MIL-53(Al)solht [27].

measurements. The weight of sample was determined before and after activation. Carbon dioxide, carbon monoxide, methane, oxygen and argon adsorption isotherms were measured both at 288 and 303 K up to 1 bar using the same procedure. The adsorption temperature was maintained (0.1 K) by circulating water from a constant temperature bath (Julabo F25, Germany). The adsorption and desorption were completely reversible, and it is possible to remove the adsorbed gases by simple evacuation. The adsorption data are tted in Virial equation. The values for Henrys constant were determined from these data. Heat of adsorption in the low pressure region and adsorption selectivity was determined from the adsorption data at 303 K.

4 Results and discussion The diffraction patterns of the synthesized MIL-53(Al) samples (Fig. 1) showed high crystallinity with reections in the range 535, characteristics of MIL-n type MOFs. The XRD patterns of MIL-53(Al)solht was well matched with the calcined sample reported earlier by Ferey et al. [21]. The absence of peaks due to H2BDC in the PXRD pattern of MIL-53(Al)solht suggest its removal from the cavities of MIL-53(Al)as after solvent extraction method. The thermo gravimetric analysis (TGA) of MIL53(Al)solht was conducted from room temperature to 600 C. The TGA and the differential thermal analysis (DTA) plots of the sample are shown in Fig. 2. The initial weight loss below 100 C may be due to the loss of water molecules from the pores. The TGA plot indicated that the material is thermally stable up to 450 C. A sharp increase in the weight loss above 450 C indicated the collapse of MIL-53(Al)solht structure due to the removal of structural

3 Characterization The X-ray powder diffraction analysis at ambient temperature was carried out using a PHILIPS Xpert MPD system ). in the 2h range of 550 using Cu Ka1 (k = 1.54056 A Thermo gravimetric analysis was carried out from room temperature to 600 C in a TGA/DTA analyzer (Mettler Toledo) at a heating rate of 10 C/min under argon atmosphere. Fourier transform infrared spectroscopy (FTIR) of the synthesized MIL-53(Al) was performed on PerkinElmer spectrum GX FT-IR instrument as KBr pallets in the range of 4004,000 cm-1 with a resolution of 4 cm-1. The BET surface area of the synthesized MIL-53(Al)solht was measured on a static volumetric adsorption system, ASAP 2020, (Micromeritics Inc., USA) using N2 adsorption desorption isotherms at 77 K up to 1 bar pressure; activating the sample by heating (1 K min-1) to 473 K under vacuum (5 9 10-3 mmHg). The temperature and vacuum was maintained for 8 h prior to the adsorption

Intensity (a. u.)

H2BDC

MIL-53 (Al)sol ht

MIL-53 (Al)as
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Fig. 1 PXRD patterns of as-synthesized, MIL-53(Al)as, MIL53(Al)solht and terephthalic acid (H2BDC)

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Fig. 2 Thermo gravimetric analysis (TGA) and the differential thermal analysis (DTA) plots of MIL-53(Al)solht

Fig. 4 N2 adsorptiondesorption isotherms of MIL-53(Al)solht at 77 K

MIL-53(Al)sol ht % transmittance (a. u.)

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Fig. 3 FTIR spectra of as-synthesized, MIL-53(Al)as and MIL53(Al)solht

BDC linkers from the framework. The DTA plot also show two endothermic peaks with maximum at 57 and 500 C respectively. The Fourier transform infrared spectra of the MIL53(Al)as and MIL-53(Al)solht (Fig. 3) exhibit vibration bands in the region 1,4001,700 cm-1 for the carboxylic functional group [21]. It also exhibits bands at 1,608 and 1,512 cm-1 corresponds to COO- asymmetric stretching whereas the bands at 1,435 and 1,417 cm-1 are attributed to COO- symmetric stretching. The additional absorption band at 1,669 cm-1 was due to the COOH group of unreacted BDC molecules trapped in the cavities of MIL53(Al)as as also seen by PXRD data. The FTIR spectrum of MIL-53(Al)solht was quite similar to MIL-53(Al)as except the absence of band at 1,669 cm-1 which conrmed the

removal of free BDC molecules by solvent extraction method. The N2 adsorptiondesorption isotherms of MIL53(Al)solht are (Fig. 4) Type I according to the IUPAC classication which is characteristic for microporous materials. The isotherms showed no hysteresis with complete desorption of the nitrogen adsorbed at 77 K, on reducing the pressure. The BET surface area of MIL53(Al)solht was found to be 1,235 m2/g and comparable to the reported value (1,140 m2/g) [21]. The Langmuir surface area of the MIL-53(Al)solht was 1,627 m2/g. It has been reported that microporous materials such as metal organic frameworks exhibit absolute and excess adsorption capacities for various gases [28, 29]. The absolute adsorption capacity for an isotherm reaches the saturation at high pressure and then remains constant; the material showing excess adsorption isotherm exhibits a maximum and then there is decrease in the gas adsorption at high gas densities. Typically at supercritical temperatures, the inection of the excess adsorption isotherm is observed only at very high pressure. There was no excess adsorption observed in these system and the observed adsorption isotherms of CO2, CH4, CO, N2, Ar and O2 on MIL-53(Al)solht at 288 and 303 K up to 850 torr are absolute in nature. The absolute adsorption isotherms of CO2, CH4, CO, N2, Ar and O2 on MIL-53(Al)solht at 288 and 303 K (Fig. 5) and their adsorption capacities at 288 and 303 K (Table 1) follows the order, CO2[CH4[CO[N2[Ar[O2. The adsorption isotherm of carbon dioxide showed a step at 168.5 mmHg pressure, which is not common for microporous materials, may be due to the breathing effect of MIL-53(Al)solht framework upon adsorption of carbon dioxide [23]. When the rst portion of the CO2 gets adsorbed, the hostguest interactions force the channel to

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Fig. 5 Adsorption isotherms of CO2, CH4, CO, N2, Ar and O2 on MIL-53(Al)solht (a) at 303 K up to 860 mmHg and (b) at 288 K up to 860 mmHg

close and the framework to shrink. The lower adsorption capacity (12 cc/g) of carbon dioxide at low pressure up to 168.5 mmHg was attributed to the shrinkage of MIL53(Al)solht framework. On further adsorption of CO2, the framework re-opens the channels and more CO2 get adsorbed. The sharp rise in the carbon dioxide adsorption capacity in the 168.5339.3 mmHg pressure range conrms the breathing character of MIL-53(Al)solht framework upon carbon dioxide adsorption. The hydroxyl groups located at the metaloxygen-metal links (l-OH groups) are responsible for this unusual breathing effect in MIL53(Al)solht framework. However, the adsorption isotherms obtained for other studied gases are typical of those obtained with microporous materials such as zeolites and activated carbons. The difference in adsorption behaviors of CH4 and CO2 in MIL-53 framework was explained based on the quadrupole moments of the adsorbate [26]. The weak quadrupole interactions between CO2 and hydroxyl groups of MIL-53(Al) framework may be

responsible for the unusual breathing character on CO2 adsorption in MIL-53(Al)solht framework. The probe molecules CO2, CO, N2 and O2 possess signicant quadrupole moments whereas CH4 and Ar have zero quadrupole moment (Table 1). Although the adsorbate molecules CO, N2 and O2 are having specic quadrupole moments, their adsorption capacities are less than that of methane. Both CH4 and Ar have zero quadrupole moment but the adsorption capacity of CH4 is more than that of Ar. In case of N2, O2 and Ar, the quadrupole moment of N2 is higher than that of O2 nearly by a factor of 3 and the quadrupole moment of Ar is zero but their adsorption capacities are nearly the same. The higher adsorption capacities of CO2 in MIL-53(Al)solht compared to other adsorbate gases could be due to its high quadrupole moment. The difference in the adsorption capacities of CH4, CO, N2, Ar and O2 cannot be explained based on their quadrupole moments. Another important parameter which contributes to the adsorbent-adsorbate interactions is the polarizability (a) of the corresponding adsorbate gases which may be responsible for the difference in the adsorption capacities of CH4, CO, N2, Ar and O2. The order of polarizabilities of different adsorbate gases are as CO2[CH4[CO[N2[Ar[O2 (Table 1). The polarizability of CH4 is more compared to other gases CO, N2, Ar and O2. There is signicant difference in the values of polarizabilities for CH4 and Ar. N2, Ar and O2 have almost similar polarizability. The higher adsorption capacity for CH4 compared to the other adsorbate gases may be due to its high polarizability. Although CH4 and Ar have no specic quadrupole moment, the difference in their polarizability may be responsible for the higher adsorption capacity of CH4 compared to Ar. Though there is a signicant difference in the quadrupole moments of N2, Ar and O2, their polarizability are nearly the same, and hence these gases have the similar adsorption capacities in MIL53(Al)solht. The adsorption capacities of CO2, CH4, CO, N2, O2 and Ar on MIL-53(Al)solht at 288 and 303 K follow the order of their polarizability rather than their quadrupole moment values. The Henrys law constant helps to determine the interactions between the adsorbate molecules and adsorbent surface at innite dilution; and the Virial isotherm provides a simple method for determining the Henrys law constant. The adsorption isotherm data was tted to the Virial equation [30]. The Henrys constant, KH, and heat of adsorption in the Henrys law region were calculated by the standard procedures [31]. The adsorbate-adsorbent interactions are dispersive in MIL-53(Al)solht, these interactions in turn depend on the dispersion of adsorbate molecules on the MIL-53(Al)solht surface which leads to higher adsorption capacities. The Henrys constant represents the extent of the adsorbate-

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Volume adsorbed (cc/g)

J Porous Mater (2011) 18:205210 Table 1 Adsorption capacity, quadrupole moment, polarizability, Henrys constant and heat of adsorption of the adsorbate gases Adsorbate gas Volume adsorbed (cc/g) 288 K CO2 CH4 CO N2 Ar O2 56.5 19.9 9.2 7.1 5.8 5.5 303 K 51.3 13.5 6.8 5.1 3.9 3.1 -13.71 0.00 -6.92 -4.91 0.00 -1.33 29.1 25.9 19.5 17.4 16.4 15.8 4.0 1.77 0.79 0.63 0.46 0.45 Quadrupole moment (91040 cm2) Polarizability (910-25 cm3) Henrys constant (cm3/g mmHg) 9 10-2

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Heat of adsorption in Henrys region (kJ/mol) 26.4 18.3 16.4 15.9 15.1 14.5

adsorbent interactions, more the value of Henrys constant for a particular adsorption process, higher will be the sorption capacity. The adsorption capacities and Henrys constants for CO2, CH4, CO, N2, O2 and Ar on MIL53(Al)solht are given in the Table 2. The heat of adsorption (DH) at low coverage is related to the sorbate-sorbent interaction potential (/) by DH / RT F T 1

aA=B Volume adsorbedA =Volume adsorbedB

where F (T) is the electric eld strength arises due to the vibrational and translational energies of the adsorbate molecule. For ambient temperature, DH & /. From Eq. 1 at ambient temperature in the low pressure region i.e. in the Henrys region, the heat of adsorption is directly proportional to the adsorption capacity of that particular adsorbate and hence more is the adsorption capacity more is the DH value for that particular adsorbate. The adsorption capacities and DH values of adsorbate molecules CO2, CH4, CO, N2, O2 and Ar on MIL-53(Al) are also given in Table 2. These values suggest that DH values of adsorbate molecules CO2, CH4, CO, N2, O2 and Ar on MIL-53(Al)solht adsorbent follows the similar trend i.e. CO2[CH4[CO[N2[Ar[O2. The adsorption selectivity of a gas A over gas B was calculated as

MIL-53(Al)solht showed high selectivity towards CO2 over O2, Ar, N2, CO and CH4 (Table 2). The order of Adsorption selectivity towards CO2 over O2, Ar, N2, CO and CH4 is as follows: CO2/O2[CO2/Ar[CO2/N2[CO2/CO[CO2/ CH4. Table 3 shows the comparison of maximum adsorption capacities of gases and volumetric equilibrium selectivities CO2/N2, CO2/CH4 and CO2/O2 of MIL-53 (Al) with other neutral framework materials such as activated carbons. The MIL-53(Al)solht provides higher CO2/O2 (16.6) and CO2/N2 (10.1) selectivities as compared to other carbonaceous materials indicated that MIL-53(Al)solht can be prospective absorbent for the separation of N2 and O2 from air via pressure swing adsorption. Furthermore, MIL53(Al)solht can be potentially used for CO2 recovery from ue gases due to its high CO2/N2 selectivity. The selectivity for CO2 over CH4 (3.8) for MIL-53(Al)solht indicates its suitability for separation of CO2 from CH4 and CO2 gas mixtures in natural gas streams.

5 Conclusions Porous aluminum terephthalate MIL-53(Al)solht was synthesized using hydrothermal method and puried by solvent extraction method. The order of adsorption capacities for the adsorbate gases studied were CO2[CH4[CO[ N2[Ar[O2. The order of the adsorption capacities of the adsorbate gases CO2, CH4, CO, N2, O2 and Ar on MIL53(Al)solht dependent on their polarizabilities. The low heat of adsorption and high selectivity values of CO2 over O2, Ar, N2, CO for MIL-53(Al)solht suggests that it can be used as a potential adsorbent material for gas separation process. MIL-53(Al)solht can be used to separate CO2 from N2/O2 due to its high adsorption selectivity for CO2 over N2/O2. MIL-53(Al)solht can also be used as good adsorbent material for separating CO2 from CO and CH4 from O2.

Table 2 Adsorption selectivities on MIL-53(Al)solht at 303 K Adsorbate gas CO2/O2 CO2/Ar CO2/N2 CO2/CO CO2/CH4 CH4/O2 CH4/Ar CH4/N2 Selectivity 16.6 13.1 10.1 7.6 3.8 4.4 3.4 2.7 Adsorbate gas CH4/CO CO/O2 CO/Ar CO/N2 N2/O2 N2/Ar Ar/O2 O2/N2 Selectivity 2.0 2.2 1.7 1.3 1.6 1.3 1.3 0.6

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Table 3 Comparison of maximum adsorption capacities of gases and volumetric equilibrium selectivities with other carbonaceous materials Material Maximum adsorption capacity (cc/g) Selectivity CO2 Ordered mesoporous carbon (Silica/sucrose SBA-15) 9.2 CH4 4.4 7.5 2.1 3.0 15.6 13.5 N2 2.4 9.2 2.3 1.3 6.5 5.1 O2 2.7 12.5 9.5 0.5 8.3 3.1 CO2/CH4 CO2/N2 CO2/O2 2.07 2.01 10.05 3.56 3.26 3.8 3.80 1.64 9.20 7.99 7.79 10.1 3.36 1.21 2.31 21.16 6.15 16.6 Zhou et al. [32] Adinata et al. [33] Daud et al. [34] Aroua et al. [35] Aroua et al. [35] This study References

Benzene deposited on chemically activated oil palm 15.2 shell based activated carbon Benzene deposited on physically activated oil palm shell based activated carbon Virgin palm shell based activated carbon Poly ethylene mine impregnated palm shell based activated carbon MIL-53(Al) 21.9 10.7 51.1 51.3

Acknowledgments The authors wish to thank Analytical Science Discipline, CSMCRI, for their technical assistance in instrumental analysis. The authors also acknowledge the nancial support of GNFC, Bharuch and CSIR under network project NWP 010. PR and KPP thanks CSIR, New Delhi for nancial support in the form of senior research fellowship. PR is grateful to Mr. Sunil A. P. for some fruitful discussions.

References
1. C.T. Chou, C.Y. Chen, Sep. Purif. Technol. 39, 51 (2004) 2. P. Harlick, F.H. Tezel, Microporous Mesoporous Mater. 76, 71 (2004) 3. K.T. Chue, J.N. Kim, Y.J. Yoo, S.H. Cho, R.T. Yang, Ind. Eng. Chem. Res. 34, 591 (1995) 4. M. Frere, G.P. Weireld, R. Jadot, J. Porous. Mater. 5, 275 (1998) 5. P.J.E. Harlick, A. Sayari, Ind. Eng. Chem. Res. 45, 3248 (2006) 6. Z. Yong, V. Mata, A.E. Rodrigues, Ind. Eng. Chem. Res. 40, 204 (2001) 7. E.L.G. Oliveira, C.A. Grande, A.E. Rodrigues, Sep. Purif. Technol. 62, 137 (2008) 8. U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastre, J. Mater. Chem. 16, 626 (2006) 9. G. Ferey, Chem. Soc. Rev. 37, 191 (2008) 10. S. Horkie, M. Dinca, K. Tamaki, J.R. Long, J. Am. Chem. Soc. 130, 5854 (2008) 11. N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. OKeeffe, O.M. Yaghi, Science 300, 1127 (2003) 12. G. Calliga, J.A. Botas, M.G. Orcajo, M.S. Sanchez, J. Porous. Mater. 17, 91 (2010) 13. M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. OKeeffe, O.M. Yaghi, Science 295, 469 (2002) 14. S. Ma, D. Sun, J.M. Simmons, C.D. Collier, D. Yuan, H.C. Zhou, J. Am. Chem. Soc. 130, 1012 (2008) 15. Y.S. Bae, K.L. Mulfort, H. Frost, P. Ryan, S. Punnathanam, L.J. Broadbelt, J.T. Hupp, R.Q. Snurr, Langmuir 24, 8592 (2008)

16. L. Bastin, P.S. Barcia, E.J. Hurtado, J.A.C. Silva, A.E. Rodrigues, B.A. Chen, J. Phys. Chem. C. 112, 1575 (2008) 17. R.E. Morris, P.S. Wheatley, Angew. Chem. Int. Ed. 47, 4966 (2008) 18. Y. Li, R.T. Yang, Langmuir. 23, 12937 (2007) 19. J.Y. Lee, D.H. Olson, L. Pan, T.J. Emge, J. Li, Adv. Funct. Mater. 17, 1255 (2007) 20. F. Millange, C. Serre, G. Ferey, Chem. Commun. 8, 822 (2002) 21. T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G. Ferey, Chem. Eur. J. 10, 1373 (2004) 22. C. Serre, F. Millange, C. Thouvenot, M. Nogues, G. Marsolier, D. Louer, G. Ferey, J. Am. Chem. Soc. 124, 13519 (2002) 23. P.L. Llewellyn, S. Bourrelly, C. Serre, Y. Filinchuk, G. Ferey, Angew. Chem. Int. Ed. 45, 7751 (2006) 24. G. Ferey, M. Latroche, C. Serre, F. Millange, T. Loiseau, A.P. Guegan, Chem. Commun. 24, 2976 (2003) 25. S. Bourrelly, P.L. Llewellyn, C. Serre, F. Millange, T. Loiseau, G. Ferey, J. Am. Chem. Soc. 127, 13519 (2005) 26. C. Serre, S. Bourrelly, A. Vimont, N.A. Ramsahye, G. Maurin, P.L. Llewellyn, M. Daturi, Y. Filinchuk, O. Leynaud, P. Barnes, G. Ferey, Adv. Mater. 19, 2246 (2007) 27. R. Phani, D. Patil, K.P. Prasanth, R.S. Somani, R.V. Jasra, H.C. Bajaj, J. Porous. Mater. doi:10.1007/s/10934-009-9320-5 28. F.O. Mertens, Surf. Sci. 603, 1979 (2009) 29. A.G. Wong-Foy, A.J. Matzjer, O.M. Yaghi, J. Am. Chem. Soc. 128, 3494 (2006) 30. S. Himeno, T. Tomita, K. Suzuki, S. Yoshida, Microporous Mesoporous Mater. 98, 62 (2007) 31. S.A. Peter, J. Sebastian, R.V. Jasra, Ind. Eng. Chem. Res. 44, 6856 (2005) 32. L. Zhou, X. Liu, J. Li, N. Wang, Y. Zhou, Chem. Phys. Lett. 413, 6 (2005) 33. D. Adinata, W.M.A.W. Daud, M.K. Aroua, Fuel Proc. Technol. 88, 599 (2007) 34. W.M.A.W. Daud, M.K. Ahmad, M.K. Aroua, Sep. Purif. Technol. 57, 289 (2007) 35. M.K. Aroua, W.M.A.W. Daud, C.Y. Yin, D. Adinata, Sep. Purif. Technol. 62, 609 (2008)

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